Polymers prepared from organic polyisocyanates or polyisothiocyanates and amides of certain ketimine blocked polyamines and carboxylic acids



United States Patent.

No Drawing. Original application Oct. 24, 1966, Ser. No.

588,772. Divided and this application Apr. 31, 1969, Ser. No. 829,840Int. Cl. C08g 22/02, 22/04 US. Cl. 260--77.5 Claims ABSTRACT OF THEDISCLOSURE New compositions of matter are prepared by reacting apolyamine having at least one free secondary amine group and at leasttwo ketimine blocked primary amine groups with a carboxylic acidcompound in substantially equivalent amounts to form an amide linkage orlinkages from the secondary amine group or groups and the carboxyl groupor groups of the carboxylic acid compound.

Polymers are prepared by reacting the resulting derivatives with anorganic polyisocyanate or polyisothiocyanate in the presence of water.

This application is a division of Ser. No. 588,772, filed Oct. 24, 1966.h

The present invention relates to derivatives of certain polyaminecompounds and carboxylic acids. More particularly, it relates toderivatives of carboxylic acids (or the anhydrides, acid halides oresters thereof) and certain polyamine compounds in which the primaryamine groups are blocked by ketimine groups. It also relates to thepreparation of polymers from such derivatives and organicpolyisocyanates or polyisothiocyanates.

It has previously been proposed to prepare polyureas from compositionscomprising polyisocyanates and polyamines wherein the primary aminegroups are blocked by ketimine groups. Such compositions were found tobe relatively stable in the absence of moisture. Finally cured or formedpolyurea products are prepared therefrom by simple exposure to moisturewhich converts the blocked polyamine compound to the free polyaminewhich is then capable of reacting with the polyisocyanate to form thepolyurea polymer. Such one-component systems were found to be veryuseful. Thus in using said compositions. it is possible to cast a filmof the mixture and expose it to moisture from the atmosphere to form apolyurea coating which becomes tack-free in a relatively short period oftime. It is also possible to form thicker castings of the saidcompositions and, upon exposure to moisture, curing likewise takesplace. Such systems may also be used for the preparation of roomtemperature curing caulking compounds, sealants and adhesives.

While the use of the ketimine blocked polyamines allows a reasonabledegree of control over the polyamine-polyisocyanate reaction, theproperties of the resulting polyurea polymers are not always completelysatisfactory for any particular use. The properties are dependent mainlyon the particular polyamine and polyisocyanate employed. It would bedesirable to be able to have control over the polyaminepolyisocyanatereactoion and yet be able to tailor the properties of the resultingpolyurea polymers.

It is, therefore, an object of the present invention to provide novelderivatives of certain polyamine compounds and carboxylic acids. Anotherobject of the invention is to provide such derivatives of carboxylicacids (or the 3,523,925 Patented Aug. 11, 1970 anhydrides, acid halidesor esters thereof) and certain polyamine compounds in which the primaryamine groups are blocked by ketimine groups. A further object of theinvention is to provide novel polymers prepared from such derivativesand organic polyisocyanates or polyisothiocyanates. These and otherobjects will become apparent from the following detailed description ofthe invention.

We have now discovered novel derivatives of polyamine compounds havingthe primary amine groups blocked by ketimine groups and having at leastone secondary amine group, said derivatives being prepared by reactingthe said polyamines with a suflicient amount of a carboxylic acidcompound to react with the secondary amine group or groups of saidpolyamine. Such derivatives are particularly useful for reaction withpolyisocyanates or polyisothiocyanates to provide polymers of highutility. Our novel derivatives allow the tailoring of the properties ofthe polymers prepared therefrom through the appropriate selection of thecarboxylic acid moiety introduced therein.

Any polyamine capable of reacting with an organic polyisocyanate andhaving at least one secondary amine group may be used in the preparationof the derivatives of the present invention. Preferred polyamines arethe alkylene polyamines and the substituted alkylene polyamines.Especially preferred polyamines are selected from those having thefollowing formula:

where R is a difunctional aliphatic group containing from 2 to about 48carbon atoms and n is an integer of 1 to about 20. R may represent thesame or different radicals in any one polyamine compound. Where thepolyamines contain two or more secondaiy amine groups, one or more ofsaid groups may have the hydrogen replaced by an aliphatic group, i.e.methyl, propyl, butyl, decyl, hexadecyl, hexenyl, octenyl, tridecenyl,octadecyl, undecynyl and the like. Inert or non-interfering groups suchas Cl, nitro and the like may be present on the group R or the describeds'ubstituent replacing the hydrogen of one or more secondary aminegroups. The polyamines must contain at least one free secondary aminegroup,

prior to the preparation of the derivatives of our invention.

Particularly preferred polyamines are those having the formula as setforth above wherein R is an aliphatic hydrocarbon group and n is aninteger of 1 to 3. It is still more preferred that R is an alkylenegroup of 2-6 carbon atoms.

Typical of the amines which may be used are diethylene triamine,triethylene tetramine, etc., and the corresponding propylene, butylene,etc. amine.

The primary amine groups in the polyamine compounds are converted toketimines by reaction with ketones. Such ketones may have the followingstructural formula:

wherein R and R are organic radicals and are each substantially inert tothe ketimine formation'reaction. Preferably R and R are short chainalkyl groups (1 to 4 carbon atoms). Preferred compounds are lowmolecular weight ketones that are volatile so that an unreacted excessthereof may easily be removed by conventional distillation practiceswhen the reaction is completed. Such vola. tile compounds are alsopreferred so that when the deriva- Preferred examples of ketones includeacetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone,methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone,ethyl isopropyl ketone, cyclohexanone, cyclopentanone, acetophenone,propiophenone, and the like. Especially preferred ketones are acetone,methyl ethyl ketone and methyl isobutyl ketone.

The derivatives of the present invention are prepared from the polyaminecompounds having at least one free secondary amine group and having theprimary amine groups thereof blocked with ketimine groups by reactingsame with a carboxylic acid compound under amide forming conditions.Thus the free secondary amine groups are converted to amide groups.

Any mono, di or higher carboxylic acid can be used in the preparation ofthe derivatives of the invention. Such acids preferably contain from 1to about 40 carbon atoms. Representative monocarboxylic acids areformic, acetic, lactic, propionic, butyric, benzoic, valeric, caproic,enanthylic, caprylic, pelargonic, capric, undecyclic, lauric, tridecoic,myristic, pentadecanoic, palmitic margaric, stearic, nondecylic,arachidic, behenic, carnaubic, hyenic, carbocerie, cerotic, lacceroic,melissic, montanic, psyllic, acrylic, crotonic, isocrotonic vinylacetic,methacrylic, tiglic, angelic, senecioic, hexenic, teracrylic, hypogeic,oleic, elaidic, erncic, brassidic, sorbic, linoleic, linolenic,propiolic, tetrolic, pentinoic, amylpropiolic, palmitolic, stearolic,behenolic, cinnamic, and the like. Representative dicarboxylic andhigher acids are adipic, citraconic. fumaric, glutaric, maleic, malic,malonic, oxalic, salicylic. succinic, tartaric, phthalic, hebacic,suberic, azelaic, tere- .phthalic, pimelic, isophthalic, polymeric fatacids and the like. It is, of course, to be understood that in additionto the carboxylic acids referred to, other saturated or un-.

saturated carboxylic acids having straight or branched chains may beused, as well as acids having various substituents such as cl, nitro,hydroxyl and the like. Also the corresponding acid chlorides, anhydridesand esters of the said carboxylic acids may be employed. Preferably theesters, if used, are prepared from alcohols containing less than about 8carbon atoms-Le. methyl, ethyl, propyl and the like.

One especially preferred group of carboxylic acids to be employed inpreparing the derivatives of the present invention are the polymeric fatacids. The term polymeric fat acid refers to a polymerized fat acid. Theterm fat acid as used herein refers to naturally occurring and syntheticmono-basic aliphatic acids having hydrocarbon chains of 8-24 carbonatoms. The term fat acids, therefore, includes saturated, ethylenicallyunsaturated and acetylenically unsaturated acids. Polymeric fat radicalis generic to the divalent, trivalent and polyvalent hydrocarbonradicals of dimerized fat acids, trimerized fat acids and higherpolymers of fat acids, respectively. These divalent and trivalentradicals are referred to herein as dimeric fat radical and trimeric fatradical."

The saturated, ethylenically unsaturated, and acetylenically unsaturatedfat acids are generally polymerized by somewhat diiferent techniques,but because of the functional similarity of the polymerization products,they all are generally referred to as polymeric fat acids.

Saturated fat acids are difiicult to polymerize, but

polymerization can be obtained at elevated temperatures with a peroxidicreagent such as di-t-butyl peroxide. Because of the low yields ofpolymeric products, these materials are not commercially significant.Suitable saturated fat acids include branched and straight chain acidssuch as caprylic acid, pelargonic acid, capric acid, lauric acid,myristic acid, palmitic acid, isopalmitic acid, stearic acid, arachidicacid, behenic acid and lgnocerc acid.

The ethylenically unsaturated acids are much more readily polymerized.Catalytic or non-catalytic polymerization techniques can be employed.The non-catalytic polymerization generally requires a highertemperature. Suitable agents for the polymerization include acid oralkaline clays, di-t-butyl peroxide, boron trifiuoride and other Lewisacids, anthraquinone, sulfur dioxide and the like. Suitable monomersinclude the branched and straight chain, polyand monoethylenicallyunsaturated acids such as 3-octenoic acid, ll-dodecenoic acid, lindericacid, lauroleic acid, myristoleic acid, tauzuic acid, palmitoleic acid,petroselinic acid, oleic acid, elaidic acid, vaccenic acid, gadoleicacid, cetoleic acid, nervonic acid, linoleic acid, linolenic acid,eleostearic acid, hiragonic acid, moroctic acid, timnodonic acid,eicosatetraenoic acid, nisinic acid, scoliodonic acid and chaulmoogricacid.

Acetylenically unsaturated fat acids, such as isanic and isanolic acids,can also be polymerized to give polymeric acids which can be used. Theacetylenically unsaturated acids occur only rarely in nature and areexpensive to synthesize. Therefore, they are not currently of commercialsignificance.

Although any one of the above-described saturated, ethylenicallyunsaturated and acetylenically unsaturated fat acids may be used toprepare the polymeric fat acids, it is generally the practice in the artto polymerize mixtures of acids (or the simple aliphatic alcoholestersi.e., the methyl esters) derived from the naturally occurringdrying and semi-drying oils. Suitable drying and semidrying oils includesoybean, linseed, tall, tung, perilla, oiticia, cottonseed, corn,sunflower, dehydrated castor oil and the like. Also, the most readilyavailable acids are oleic and linoleic and thus they are preferredstarting materials for the preparation of the polymeric fat acids.Relatively pure dimerized fat acids can be obtained from mixturescontaining monomer, the dimerized fat acids, trimerized fat acids andhigher polymers by high vacuum distillation or solvent extraction. Anyof the described unsaturated polymeric fat acids can be hydrogenatedprior to the use thereof in the present invention.

The derivatives are prepared by heating a mixture of the ketimineblocked polyamine with the carboxylic acid compound to a temperaturesufficiently high to form the amide linkage Thus, for example, whenusing a carboxylic acid, the mixture should preferably be heated toabove C. and more preferably to C. and above. Temperatures of aboveabout 300 C. hould be avoided in most instances because of possibledegradation of the resulting derivative. The reaction is also preferablycarried out under conditions such that by-product water, HCl or alcoholsformed during the reaction are removed from the reaction mixturei.e. bydistillation. And it is also preferred to carry out the reaction in thepresence of a solvent. Such solvent should not react with either thecarboxylic acid compound or the ketimine blocked polyamine. Hydrocarbonsolvents such as benzene, toluene, xylene, cumene, ethylbenzene, heptaneand the like are entirely suitable and preferred.

The carboxylic acid (or the anhydrides, acid chlorides 0r estersthereof) is used in an amount about equivalent to the equivalents offree secondary amine groups of the polyamine. In this respect, if thepolyamine contains one free secondary amine group and the carboxylicacid is a monocarboxylic acid, one mole of the polyamine is reacted withone mole of the acid. If the polyamine contains two free secondary aminegroups and the carboxylic acid is a monocarboxylic acid, one mole of thepolyamine would be reacted with two moles of the monocarboxylic acid. Ifthe polyamine has one free secondary amine group and the carboxylic acidis a dicarboxylic acid, two moles of the polyamine would be reacted withone mole of the dicarboxylic acid. It is thus apparent that the ratio ofreactants varies as to the number of free secondary amine groups of thepolyaminei.e. one, two, three or moreand as to whether the carboxylicacid compound is mono, di, tri or higher. An excess of the ketimineblocked polyamine can be used in the formation of the derivative. Aftercompletion of the reaction, the said excess can be removed from thederivative such as by distillation.

The derivatives of our invention are complex materials. In this respectthey comprise a residue of a polyamine, 2 or more (preferably less thanabout 50) ketimine blocked primary amine groups and 1 or more(preferably less than about 50) amide groups derived from the secondaryamine group or groups of the polyamine and carboxylic acid compounds. Insome of the preferred and simpler aspects, the derivatives can bedefined structurally. Thus when the polyamine has only one freesecondary amine group and the carboxylic acid compound is monoordi-functional or when the polyamine has more than one free secondaryamine group and the carboxylic acid compound is mono-functional, thederivatives can be defined by the following idealized, structuralformulae:

where R and R are as defined above, n is an integer of at least 2, m. isan integer of at least 1,

is the residue of a polyamine exclusive of the ketimine blocked primaryamine groups and the amide linked secondary amine nitrogen, X is whereMA is the residue of a monocarboxylic acid, and is I where DA is theresidue of a dicarboxylic acid. Where the polyamine contains two or moresecondary amine groups and the carboxylic acid compound is di, tri or Amixture of 146 g. (1.0 mole) adipic acid, 700 g. xylene and 540 g. (2.02mole) of the diketimine made from diethylenetriamine and methyl isobutylketone was heated at reflux under a nitrogen atmosphere in a 2000 ml.round bottom flask equipped with a stirrer, reflux condenser and Barretttrap. The reaction mixture was refluxed for 20 hours during which time41 ml. of water was removed by azeotropic distillation. At the end ofthe said reaction period (no more water being formed), the liquidportion of the reaction mixture was separated and stripped of solvent byheating under vacuum leaving 465 g. of residue. Unreaeted diketimine wasdistilled from the residue to a pot temperature of 196 C. (at 0.7 mm.Hg) leaving 184 g. of derivative. The derivative had an amine number of384 and its infrared spectrum taken in carbon tetrachloride showed bandsat 6.0 and 6.16 microns characteristic of ketimines and disubstitutedamides, respectively. The derivative had the following structure:

CH3 CH3 C=NCH2CHrNCHzCH2N-=C isobutyl (3:0 isobutyl 2); CH3 (|3=O CH:

C=NCH2CHzl ICH2CH2N=C isobutyl isobutyl EXAMPLE B Example A wasessentially repeated except that 267 g. 1.0 mole) of the diketimine, 500g. xylene and 282 g. (.5 mole) of hydrogenated, distilled dimerized fatacid (percent dimer-93.5, percent monomer5.5, percent trimer1.0; acidnumber192.9; iodine value18.6) were employed. The dimerized fat acid wasprepared by polymerizing the mixture of fat acids derived from tall oiland consisted mainly of a mixture of dimerized linoleic and oleic acids.The resulting product had an amine number of 254 and its infraredspectrum showed bands correseponding to ketimine and disubstitutedamide. Theproduct consisted mainly of the derivative having thefollowing structure:

isobutyl 0:0 isobutyl CH3 3 0 CHa c=N-o H2O Hz-h'T-C Hie Hz-N- oisobutyl isobutyl where D is the divalent hydrocarbon radical of thestarting hydrogenated dimerized fat acid.

EXAMPLE C In a 2000 ml., three-neck flask equipped with magneticstirrer, thermometer, nitrogen purge and reflux condenser vwith a Barrettrap was placed 282 g. (0.5 mole) hydrogenated, distilled dimerized fatacid (as used in Example B), 534 g. (2.0 mole) diketimine (as used inExamples A and B), 500 ml. xylene. The mixture was heated at reflux C.)for 10 hours as water was distilled off. After the azeotropicdistillation of water was completed, xylene was distilled off underreduced pressure. Finally, unreacted diketimine was distilled off up toa reaction temperature of 198 C. (at 1 mm. Hg). There was obtained 491g. of derivative which was a viscous liquid. Its infrared spectrumshowed 'bands corresponding to disubstituted amide and ketimine. Thederivative had the same structure as the derivative of Example B.

EXAMPLE D In a 2000 ml. flask as used in Example C was placed 451.5 g.(2.14 mole) of the diketimine made from diethylenetriamine and methylethylketone, 305.0 g. (0.54 mole) of hydrogenated, distilled dimerizedfat acid (asused in Example B) and 500 ml. xylene. The mixture washeated at reflux (141-147 C.) for 6 hours as water distilled off Afterthe azeotropic distillation of water was completed, xylene was distilledoff until the reaction temperature reached 165 C. Finally, a vacuum Wasapplied and residual xylene and excess diketimine were distilled E.These was obtained 460 g. of derivative having an amine number of 238.Infrared analysis showed bands corresponding to ketirnine anddisubstituted amide absorption. The derivative had the followingstructure:

where D is the divalent hydrocarbon radical of the starting dimerizedfat acid.

EXAMPLE E A mixture of 148 g. (0.5 mole) of the diketimine made fromdi-(3-aminopropyl)amine and methyl isobutyl ketone, 141 g. (0.25 mole)of hydrogenated, distilled dimerized fat acid (as used in Example B) and50 ml. xylene was charged to a 500 ml. round bottom flask equipped withthermometer, reflux condenser, Barrett trap and magnetic stirrer. Thereaction mixture was refluxed for 7%. hours while removing water formedin the reaction. After completion of the reaction, the reaction productwas stripped of xylene by heating at reduced pressure. There wasobtained 265 g. of derivative having an amine number of 195. Thederivative had the following structure:

sobutyl isobutyl isobutyl isobutyl where D is the divalent hydrocarbonradical of the starting dimerized fat acid.

EXAMPLE F A mixture of 588 g. (2.2 mole) diketimine (as used in ExampleA), 564.0 g. (1.0 mole) hydrogenated, distilled dimerized fat acid (asused in Example B), and 1000 g. xylene was charged to a 3000 ml. threenecked, round bottom flask equipped with a nitrogen inlet, refluxcondenser, Barrett trap and thermometer. The reaction mixture wasrefluxed at 140-145 C. for six hours during which period 64 g. water wasremoved by distillation. After the said reaction period (no more waterbeing formed), excess xylene was stripped from the reaction productunder vacuum. There was obtained 1007 g. of derivative having an aminenumber of 274.6. The derivative had the following structure:

isobutyl isobutyl isobutyl where D is the divalent hydrocarbon radicalof the starting dimerized fat acid.

As indicated above, the derivatives of the present invention areparticularly useful for preparing polymers by reaction with organicpolyisocyanates or polyisothiocyanates and such polymers also form apart of our invention.

' Typical polyisocyanates which may be used in preparing the polymers ofthe present invention include the polymethylene diisocyanates such asethylene diisocyanate, trimethylene diisocyanate, tetramethylenediisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate,etc.; other alkylene diisocyanates, such as propylene-1,2- diisocyanate,butylene-1,2-diisocyanate, butylene 1,3-diisocyanate,butylene-2,3-diisocyanate, etc.; alkylidene diisocyanates, such asethylidene diisocyanate, butylidene diisocyanate, etc.; cycloalkylenediisocyanates, such as cyclopentylene-1,3-diisocyanate,cyclohexylene-1,4 diisocyanate, 4,4 diisocyanato bis(cyclohexyl)methane,etc.; cycloalkylidene diisocyanates, such as cyclopentylidenediisocyanate, cyclohexylidene diisocyanate, etc.; triisocyanates such as1,2,4-butanetriisocyanate, 1,3,3-pentanetriisocyanate,1,2,2-butanetriisocyanate, etc.

Examples of useful araliphatic polyisocyanates which may be used in thepresent invention include the following: p-phenylene-2,2-bis(ethylisocyanate), p-phenylene- 3,3'-bis(propyl isocyanate)p-phenylene-4,4-bis (butyl isocyanate), m-phenylene 2,2 bis(ethylisocyanate), 1,4- naphthalene-2,2-bis(ethyl isocyanate),4,4-diphenylene- 2,2'-bis(ethyl isocyanate), 4,4'diphenyleneether-2,2-bis (ethyl isocyanate) tris(2,2',2"-isocyanatoethyl)benzene,5-chlorophenylene-l,3-bis(propyl 3 isocyanate), 5methoxyphenylene-l,3-bis(propyl-3 isocyanate), 5cyanophenyene-1,3-bis(propyl-3 isocyanate) and 5-methylphenylene-1,3-bis(propyl-3 isocyanate) Typical aromatic polyisocyanateswhich may be used include tolylene diisocyanate, m-phenylenediisocyanate, naphthalene-1,4-diisocyanate, diphenylene-4,4'diisocyanato, etc.; aliphatic-aromatic diisocyanates, such as xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, 4,4 diphenylene methanediisocyanate, etc.

The corresponding polyisothiocyanates may also be used. Preferredreactants in the preparation of our polymers are the aliphatic,cycloaliphatic and araliphatic polyisocyanates. As especially preferredgroup of polyisocyanates to be employed in the present invention arethose derived from polymeric fat acids. Such polyisocyanates have thefollowing idealized, structural formula:

where y is 0 or 1, x is an integer of 2 to about 4 and R is thehydrocarbon group of polymeric fat acids. Preferably, x is 2. Thepolyisocyanates of the above formula wherein y is 0 are prepared byconverting the polymeric fat acids to the corresponding polymeric acidchlorides, reacting the acid chlorides with a metal azide to form thepolymeric acyl azides and then heating the acyl azides to produce thepolyisocyanates. This method of preparation can be convenientlyillustrated by the following equations (using a dimeric fat acid as anexample):

The polyisocyanates wherein y is I are prepared by converting thepolymeric fat acids to the corresponding polynitriles and thenhydrogenating the polynitriles in the presence of ammonia and a catalystsuch as Raney nickel to form polyamines. The polyamines are then reactedwith phosgene to give the polyisocyanates. This method of preparationcan be conveniently illustrated by the following equations (using adimeric fat acid as an example):

The polymeric fat acids useful in preparing such preferredpolyisocyanates are as described hereinabove.

be used in preparing the polymers in the form of the free isocyanate orthey may be used in the form of so-called prepolymers. These prepolymersare generally reaction productsof polyols or polyester polyols with thepolyisocyanates or polyisothiocyanates such that essentially 1 mole ofthe latter is reacted with each equivalent of hydroxyl group, theproduct thus being an isocyanate terminated prepolymer. It is to be thusunderstood that'the' terms polyisocyanate or polyisothiocyanate areintended to include prepolymers of simple polyols, polyether polyols,and polyester polyols. Typical polyols include trimethylolpropane,1,4,6-hexanetriol, glycerol, ethylene glycol, diethylene glycol,1,4-butanediol, 1,4 butenedio, 1,3 butanediol and the like. Thepolyether polyols are hydroxy terminated homopolymers and copolymers ofethylene oxide, propylene oxide, butylene oxide, and the like. Thepolyester polyols are hydroxyl terminated polymers which may be derivedfrom the above polyols and any of the typical polybasic acids used inpolyester preparations.

The polymers of our invention are prepared by simply admixing theketimine-amide derivatives with the organic polyisocyanates orpolyisothiocyanates and exposing the reaction mixture to wateri.e.moisture from the atmosphere. The reaction can be carried out in thepresence of a diluent or solvent and, if desirable, the reaction mixturecan be heated or cooled to control the rate of reaction, When coatings,films or the like are to be prepared from the compositions, it may bedesirable to include fillers or pigments and the like. Representative ofsuch materials are amorphous silicas, titanium dioxide, carbon black,chrome yellow, phthalocyanine blue and green, toluidine red,quinacridone red, green gold, toluidine yellow, iron oxide red and fireorange red. The amounts of the derivative and the polyisocyanate used inpreparing the polymers can be varied over wide limits. Preferably thederivative such condition became tack-tree ovemight. After 14 days,coatings on glass had a pencil hardness of 6B and a Sward rockerhardness of 7% and the coating on tinplate had a GE. extensibility ofover 60%. The coatings also exhibited good dry adhesion to black platesteel, cold rolled steel, polished coldrolled steel, aluminum andgranodized steel.

EXAMPLE II Example I was repeated using a coating mixture consisting of6.4 parts of the ketimine-amide derivative of Example C (0.024equivalent), 7.5 parts dimeryl isocyanate (as used in Example I) and13.9 parts mineral spirits. The resulting coatings (3 mil) becametack-free overnight and after 14 days'had a pencil hardness of 6B (glasssubstrate), a Sward rocker hardness of 6% (glass substrate) and a GE.extensibility of greater than 60% (tinplate substrate).

and polyisocyanate are used in an equivalent ratio of about 2:1 to 1:2based on the ketimine blocked primary amine groups and the freeisocyanato groups.

The following examples serve to illustrate the preparation of certainpreferred polymers and are not to be considered as limiting. All partsare by 'weight unless other- 1 'wise indicated.

EXAMPLE I A mixture of 16.1 parts of the ketimine-amide derivative ofExample A (.10 equivalent), 30 parts dimeryl isocyanate (.10 equivalent)and 46.1 parts mineral spirits (an aliphatic hydrocarbon liquidpetroleum fraction boiling from about 310 F. to 390 F.) was used to coattin and glass panels (3 mil coating). The dimeryl isocyanate had thetheoretical structural formula D (CH NCO) 2 EXAMPLE II A mixture of 13.3parts of the ketimine-amide derivative of Example B (0.05 equivalent),15 parts dimeryl isocyanate (as used in Example I) and 12.4 partsmineral spirits was used to coat various substrates (3 mil coatings).The coatings were exposed to ambient room conditions (50% relativehumidity and 70 F.) and under EXAMPLE 1V Example III was repeated usinga coating mixture consisting of 5.9 parts of the ketimine-amidederivative of Example D (0.025 equivalent), 7.5 parts dimeryl isocyanate(as used in Example" I) and 13.4 parts mineral spirits. The resultingcoatings had the same fine properties as those of Example III.

EXAMPLE V Example III was repeated using a coating mixture consisting of5.3 parts of the ketimine-amide derivative of Example B (0.02equivalent), 6.0 parts dimeryl isocyanate (as used in Example I) and11.3 parts mineral spirits. The coatings on glass and tinplate (3 mil)became tack-free overnight. The extensibility of the coatings (asmeasured on the tinplate substrate) 'was high-Le. over 60% after 7 days.The coating on the glass had a Sward rocker hardness of 3%, 5% and 6%after 1, 7 and 14 days, respectively.

EXAMPLE VI A mixture of 133 parts of the ketimine-amide derivative ofExample B (0.5 equivalent) and parts dimeryl isocyanate (as used inExample I) was placed in a container and degassed by vacuum. The mixturegelled overnight (held at 70 F. and 50% relative humidity) forming aclear elastomeric solid which had a Shore A hardness of 55.

As shown by the examples above, the polymers prepared from certain ofthe derivatives of the invention have high utility as coatings fora-variety of substrates. The properties of the polymers can, of course,be varied by the choice of polyamine, carboxylic acid compound andpolyisocyanate or polyisothiocyanate employed. The polymers also finduse in the preparation of molded articles, as adhesives and the like. f

It is to be understood that the invention is not to be limited to theexact details of operation or the exact compositions shown or describedas obvious modifications and equivalents will be apparent to thoseskilled in the art and the invention is to be limited only by the scopeof the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A polymer prepared by reacting (A) an amide having the structuralformula:

e t il).

wherein R and R are organic radicals n is an integer of at least 2, 'mis an integer of at least'l, X is 3. The polymer of claim 2 wherein theamide (A) has the structural formula:

'Where MA is the residue vof a -r'nonocarboxylic acid and is the residueof a poly'amine exclusive of the ketimine blocked primary amine groupsand the amide linked secondary amine nitrogen with (B) an organicpolyisocyanate or polyisothiocyanate in the presence of water.

2. A polymer prepared by reacting (A) an amide having the structuralformula:

wherein R and R are organic radicals, n is an'integer where DA is theresidue of dicarboxylic acid and is the residue of a polyamine exclusiveof the ketimine blocked primary amine groups and the amide linkedsecondary amine nitrogen with (B) an organic polyisocyanate orpolyisothiocyanate in the presence of water.

where D is the saturated divalent hydrocarbon radical of a mixture ofdimerized linoleic and oleic acids.

4. The polymer of claim 3 wherein the polyisocyanate has the formula hasthe formula OCNH CRCH NCO where R is the divalent hydrocarbon group of adimerized fat acid of 8-24 carbon atoms.

References Cited UNITED STATES PATENTS 6,420,800 1/1969 Haggis 260DONALD E. CZAJA, Primary Examiner 'M. J. WELSH, Assistant Examiner US.Cl. X.R.

13 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,5 3 9 5 Dated August 97 Inventor) Marwan R. Kamal, John R. Nazy, andHarold A. Wittcoff It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 67, "polyamzlnepolyisocyanate should read--polyamine-polyisocyanate--; "reactoion" should read --reaction--Column 3, line 39, "claidic" should read --elaidic--; line MI, "hebacic"should read --sebacic-- Column '4, line 8, "lgnocerc" should read--lignoceric--;

lin 53-55,

NC should read NC- line 59, "hould" should read --should-- Column 5,line 32, before the formula insert I. Column 6, line 38,

"reseponding" should read --responding--. Column 7, line 1, after"water" insert --was-- Column 8, line 29, "phenyene-" should read--phenyleneline 3 "nato" should read --nate--; line 40, "As" should read--An-- Column 10, line 8, "EXAMPLE II" should read --EXAMPLE III--.

JAN. 26,1971

mm but:

MMFladm-Jr.

mam E. 60m, 38-

L Mn Qff'w Comissioner of Patents

